Alkyl substituted benzene sulfonate



J1me 15, 19544 R. KENNEDY ETAL ,681,3

ALXYL. SUBSTITUTED BENZENE SULFONATE Filed Oct. 7, 1949 2.33m qm/q 2.23m mm c232 @2325 ON I INVENTORS ABRAHAM SCHNEIDER y ROBERT M. KENNEDY ATTORNEYS Patented June 15, 1954 ALKYL SUBSTITUTED BENZENE SULFONATE Robert M. Kennedy, Newtown Square, and Abraham Schneider, Sun Oil Company, ration of New Jersey Philadelphia,

Pa., assignors to Philadelphia, Pa., a corpo- Application October 7, 1949, Serial No. 120,076-

1 Claim.

This invention relates to new and improved detergent compositions and their process of manufacture.

Alkyl substituted benzene sulfonates are known to possess excellent detergent properties. Such sulfonates have heretofore been prepared, e. g., by alkylating benzene with chlorinated hydrocarbons using a Friedel-Crafts catalyst, such as AlCls, and sulfonating the product obtained. Another method heretofore employed involves the alkylation of benzene with an olefin, such as the tetramer of propylene, using HF or H2804 as the catalyst, followed by sulfonation of the products. In carrying out these processes, it has been found necessary to employ relatively pure aliphatic hydrocarbons in order to obtain satisfactory detergents. In some instances, to achieve a desired property, it has been necessary to prepare a substantially pure product, or a given type of prodnot within a narrow range, such as by using a single alkyl halide or a particular olefin as the alkylating agent in the preparation of the detergent. Such specific products generally exhibit an enhanced property in one respect at the expense of other desirable properties. If petroleum distillate fractions be employed, only rather narrow fractions give successful products, 1. e., fractions having a narrow boiling range. Such processes have other disadvantages, e. g., in the process requiring an alkyl halide, the halogenation of a parafiinic hydrocarbon, and especially of mixtures of hydrocarbons such as is contained in a petroleum fraction, leads to a wide variety of monoand polyhalogenated hydrocarbons, which apparently causes a large amount of undesired impurities and by-products in the final sulfonated product.

In patent application Serial No. 96,754, filed June 2, 1949, there is described and claimed a method of alkylating alkylatable aromatics with isoparaflins of from to 30 carbon atoms having at least one tertiary carbon atom per molecule which comprises subjecting a mixture of such aromatics and is oparafiins to the simultaneous action of HF and a tertiary olefin. The tertiary olefins which may be employed have an olefinic double bond and at least one side chain per molecule, and preferably has the tertiary carbon atom attached to the olefinic double bond. Isobutylene is the preferred tertiary olefin; others ineluding 2-methylbutene-2; 3-methylbutene-1; 2,3-dimethylbutene-l; 2-methylbutene-3; e-ethylhexene-l; 6-methylheptene-3, and the like, may be employed.

In patent application Serial No. 96,755, filed June 2, 1949, there is described and claimed a method of alkylating aromatics with isoparafiins having at least 1 tertiary carbon atom per molecule which comprises subjecting a mixture of such aromatics and isoparaffins to the simultaneous action of HF and a tertiary substituted aromatic. The tertiary substituted aromatics which may be employed have a tertiary carbon atom of a substituent radical attached to a carbon atom contained in an aromatic ring. Tertiary butyl benzene is the preferred tertiary substituted aromatic; others including 0-, mand ptertiary butyl toluene, the tertiary butyl xylenes, 2-phenyl-2-methylbutane; alpha tertiary butyl naphthalene, and the like, may be employed.

By the expression tertiary hydrogen is: meant a hydrogen atom attached to a tertiary carbon atom, i. e. a hydrogen atom attached to a carbon atom, which carbon atom in turn is attached to 3 other carbon atoms.

The above described alkylations are preferably performed at a temperature of from 50 C. to 200 C. and a pressure sufficient to keep the constituents of the reaction mixture in the liquid state, usually from 100 to 200 p. s. i. Also, a mole ratio of saturate to aromatics of from 1:5 to 6:1, and of tertiary olefin or tertiary substituted aromatic to aromatic plus saturate of from 1:10 to 1:1 is preferred. Excess HF is preferably employed, preferably from 1 to 8 moles for each mole of aromatic plus saturate. Time required for the alkylation varies according to the temperature employed, the reactants, and tertiary olefin employed, their concentrations, and the like, and is not considered a critical variable, it being obvious that SllfilClBIlt time should be permitted to obtain the desired product in good yields. In general, an alkylation time of 15 minutes to 2 hours attains the desired result, and when preferred reactants, catalyst, and conditions are employed, from 30 to minutes is suitable. In these alkylations it has been found characteristic of the alkylated aromatic product that the alkyl radical contains the same number of carbon atoms as did the isoparafiin. It is further characteristic that the parafiin corresponding to the tertiary olefin employed, or to the tertiary group of the tertiary substituted aromatic, is produced.

It has now been found that novel alkyl. substituted benzene sulfonates having improved detergent properties can be prepared in accordance with patent applications Serial Nos. 96,754 and 96,755, wherein a petroleum fraction boiling within the range of from about 400 F. to about 500 F. is employed as the alkylating agent. In accordance with the present invention, a petroleum fraction having a boiling range of from about 400 F. to 500 F., and having a substantial proportion of hydrocarbons having at least one tertiary hydrogen atom per molecule, is admixed with benzene, and the admixture subjected to the simultaneous action of hydrogen fluoride and a tertiary mono-olefin or a tertiary substituted aromatic hydrocarbon. By contacting hydrogen fluoride and a tertiary mono-olefin or a tertiary substituted aromatic hydrocarbon in the presence of benzene and a petroleum fraction composed largely of isopararfins having an averageof at least one tertiary hydrogen atom per molecule, a catalytic condition is established whereby the saturate hydrocarbons alkylate the benzene. The alkylated aromatic product is recovered from the reaction mixture and sulfonated, e. g., with concentrated sulfuric acid or oleum, to form a monosulfonated product. The sulfonated alkylated benzene is neutralized with an alkali, such as an aqueous solution of sodium hydroxide, and the salt so obtained is dried. This salt is the desired product.

A 400 F. to 500 F. petroleum fraction is employed in the present invention. An advantage of the present invention is that up to about 25% of the fraction may boil outside of the stated range, and good results obtained therewith. For example, a fraction wherein the last boils above 500 F., and which has an end point of about 590 F., gives good results in accordance with the present invention. The fraction employed should contain at least above about and preferably above 50%, isoparaffins having at least one tertiary hydrogen atom per molecule. Other hydrocarbons present act as diluents, and do not enter the reaction.

The 400 F. to 500 F. petroleum fraction may be a saturate fraction, 1. e., a petroleum fraction which has been dearomatized to substantially remove the aromatic hydrocarbons, or a fraction having the aromatic content normally present in such fraction. The aromatic content of the present fraction may result from the presence of aromatics in the crude, such as in a straight run fraction, or such aromatics may be formed in a cracking operation. This aromatic content is usually from about 15% to about 20%, and good results are obtained therewith in accordance with the present invention. In general, to obtain good results, the aromatic content should not exceed about and preferably is below 25%. Almost invariably a straight run or cracked 400 F.-500 F. petroleum fraction will have an aromatic content of at least 1%, and usually above 5%, and the use of fractions containing such minimum amounts of aromatics comes within the scope of the present invention. As above stated, however, a saturate petroleum fraction, i. e., a fraction containing less than about 1% aromatic hydrocarbons, may be employed with good results; it is especially surprising that removal of the aromatics from the 400 F. to 500 F. petroleum fraction is not necessary in order to prepare a remarkably superior detergent in accordance with the process of the present invention. The petroleum fraction should contain at least above 25%, and preferably above 50%, saturates having an average of at least one tertiary carbon atom per molecule, such as isoparafiins and naphthenes.

In accordance with the present invention, a petroleum fraction having an aromatic content Of less than about 35%, and a boiling range within the limits of from about 400 F. to 500 F., and having a substantial proportion of hydrocarbons having at least one tertiary hydrogen atom per molecule, is admixed with benzene, and the admixture subjected to the simultaneous action of hydrogen fluoride and a tertiary olefin or a tertiary substituted aromatic. By contacting hydrogen fluoride and a tertiary olefin or a tertiary substituted aromatic in the presence of benzene and the described petroleum fraction, a catalytic condition is established whereby hydrocarbons of the petroleum fraction having a tertiary carbon atom alkylate the benzene. The alkylated aromatic product is recovered from the reaction mixture and sulfonated, e. g., with concentrated sulfuric acid or oleum, to form a monosulfonated product. The sulfonated alkylated benzene is neutralized with an alkali, such as an aqueous solution of sodium, potassium, or ammonium hydroxide, preferably sodium hydroxide, and the salt so obtained is dried. This salt is the desired product.

In addition to the excellent detergent properties of the present substituted benzene sulfonates, as hereinafter demonstrated, a significant advantage thereof is that it is unnecessary to dearcmatize the petroleum fraction employed in the alkylation. Thus, the process of preparation of the present detergent is relatively simple and eco nomically advantageous.

The accompanying'drawing is a diagrammatic flow sheet illustrating a preferred embodiment of the pesent invention. Referring to the flow sheet, t-butyl benzene being used to illustrate the tertiary substituted aromatics which may be employed in the present process, it being understood that tertiary olefins may be substituted therefor, a 400 F.-500 F. petroleum fraction. t-butyl benzene and benzene are introduced into the system through lines 1, 2 and 4, respectively. This mixture is passed through heat exchanger 5, which may be a heater or cooler, depending on the temperature at which the alkylation is to be performed, and the mixture is then passed through line i into mixer 8, provided with a stirrer. If desired, means (not shown) to heat mixer 8 may be provided. Hydrogen fluoride is introduced into the mixer through line 0. If desired, the point of introduction of the hydrogen fluoride (line 0) and of the t-butyl benzene (line 2) may be reversed, but it is essential that these catalytic components be contacted in the presence of both the benzene and petroleum fraction. On contacting the HF and t-butyl benzene, a catalytic condition is immediately established whereby the isoparaffins and naphthenes of the petroleum fraction alkylate the benzene.

The reaction mixture leaves mixer 3 through line it, and is passed into separator ii, wherein the acid and hydrocarbon phases are separated. The acid phase, usually containing a small amount of dissolved high molecular weight of oil, is removed through line i2, and the hydrocarbon phase is passed through line it into distillation zone l5. Hydrogen fluoride is easily recoverable from the acid phase by distillation (by means not shown), and may be recycled through the process. The distillation zone l5 may advantageously consist of a plurality of such zones from which the various fractions are separated. Isobutane, formed by reduction of the t-butyl group of the t-butyl benzene, is removed through line It, Unreacted benzene is removed through line i8 and recycled through the process through line l9. Unreacted t butyl benzene is removed through line and recycled through line 2|. Any unreacted petroleum fraction is removed through line 23 and recycled through line 24. The desired alkylated aromatic product is removed through line 25, and passed into sulfonation vessel 25. Residue from distillation is removed through line 28. Oleum, used to illustrate the sulfonating agents which may be employed, is introduced into the process through line 20. Sulfonation vessel 26 may be equipped with a stirrer and means for heating or cooling (not shown). On leaving the sulfonation zone, the sulfonated product passes through line 30 into neutralization zone 3|, an aqueous solution of an alkali metal hydroxide, such as sodium hydroxide, being added through line 32. Residue is removed through line 34, and the alkyl benzene sulfonate product recovered through line 35. The product is preferably dried and pulverized by any convenient means (not shown). For example, drying may be conveniently accomplished by means of a drying oven heated to from about 100 C. to about 150 C., or by infrared rays.

The alkyl substituted benzene sulfonate, prepared in accordance with the process of the present invention, has superior properties to similar detergents heretofore known. The reason for the superiority of the present detergents over those of the prior art is not known with certainty, and it is not desired to be limited by theoretical considerations. However, it is believed that the present novel process of alkylation yields products having a novel configuration which enhances those properties necessary for good detergent action. The discovery that it is unnecessary to remove aromatics from the 400 F. to 500 F. petroleum fraction in order to produce an excellent detergent by alkylating benzene therewith in accordance with the present process is believed especially surprising, since the possible variety of alkylatable aromatics present in such fraction would be expected to lead to a wide variety of products of varying properties so that the detergency value thereof would be slight.

In order to illustrate the present invention, a series of alkyl substituted benzene sulfonates was prepared, using petroleum fractions from widely different sources boiling substantially within the range of from about 400 F. to about 500 F. and having a substantial aromatic hydrocarbon content. The alkylation was performed in .accordance with the aforementioned patent applications, the procedure being as follows: A contactor equipped with a stirrer was charged with about 150 g. of benzene, about 150 g. of the petroleum fraction, and about 222 g. of anhydrous hydrogen fluoride. Either the entire 400 F.- 500 F. petroleum fraction or a desired or convenient fraction thereof boiling within the stated ranged may be employed. The material was stirred at room temperature while about '75 g. of isobutylene was introduced over a period of 2 minutes. The stirred mixture was then heated to 100 C. for 90 minutes. The maximum pressure developed was usually about 190 p. s. i. The contactor was then cooled to about 0 C. in an ice bath and the hydrogen fluoride removed. The acid and organic layers were separated and the organic layer washed with water. The alkylated benzene product was recovered by distillation.

Sulfonation was performed using 100% sulfuric acid, asfollows: To about 30 g. of the alkyl benzene in a 3-neck flask equipped with stirrer,

dropping funnel, and calcium chloride drying tube was added dropwise about 40 g. of sulfuric acid over a period of about 30 minutes. The stirred mixture was then warmed to about 55 C. for about 1 hour and the phases allowed to separate. The lower layer was removed, diluted with ice water, and neutralized with so-- dium hydroxide. The mixture was then evaporated to dryness under infrared lamps; drying may be accomplished in an oven at about (3., the two methods of drying being equivalent. Oleum may be employed in place of sulfuric acid, such as 20% oleum, in which case substantially the same procedure is employed, except that it is preferred to cool the reaction mixture to about 0 C. during addition of the oleum. In. general, the crude alkyl benzene sulfonates prepared in accordance with the present invention are of sufficient concentration so that purification thereof is unnecessary. If desired, however, the sulfonate may be concentrated such as by extraction with alcohol.

Following the above procedure, including extraction of the crude sulfonate with alcohol to insure comparable data, the following refinery streams containing their natural aromatics, about 15-20% thereof, and having the indicated boil ing ranges, were employed in the alkylation:

1. 428-464" F. Webster straight run 2. MS-482 F. East Texas straight run 3. 482-518" F. East Texas straight run The resulting alkyl benzenes had the following properties:

Allzyl Benzene Refinery Stream Employed Molecular Boiling, Weight Range, Range 0.

428-464" F. Webster 172-253 250-340 464-48? F. East Texas 217-272 295345 482-518" F. East Texas 205280 277-340 Example 1 The detergents prepared in accordance with the present invention were tested against the standard in the actual washing of textiles. The detergents, including the standard, were com-- pounded, or built, to contain the following components: 30% of the sulfonate detergent; 40% sodium tripolyphosphate; 25% sodium sulfate; and 5% carboxymethyl cellulose.

Standard soiled cotton test swatches were agitated mechanically in both soft (2-grain) and hard (IE-grain) water using various concentra tions of the detergent composition. Z-grain water and l5-grain water refer to hardness equivalent to 2 and 15 grains, respectively, of CaCOa per gallon. Washing time was 15 minutes in water of the same hardness as" used for the wash. Detergency was determined by measurement of the reflectance of light by the sample textile swatch, using a standard reflectometer set to read 100 against magnesium oxide. Each test included 8 samples, the entire run repeated twice, and the results obtained averaged. Runs Example 4 This example demonstrates the ability of solutions of the present detergents to wet the fibres of cloth. Two 1 inch canvas disks were added to were made on the same day with the same batch 5 200 cc of a 3 solution of the built detergents g; ZE the Washmg bemg perfmme in both 2-grain and 15-grain water, and the time The following data were obtained at the indi- 2 5 i fi g i g gig gfi f gfi i g l i i a e g g Concentramons of the detergent composl' 10 from the 482-518 F. East Texas fraction was used.

With the present detergent and the standard Smwater Hard built to contain 30% sulfonate, 40% sodium tripolyphosphate, 25% sodium sulfate, and 5% car- 02% 015% boxymethylcellulose, the following data were obtained at 122 R:

428-464 F. Webster sulfonate good fair poor... very good. 446-482 F. East 48ei5ra% u1onaitgg% fair very good. good. fair. i a t r Texas sulfonate.. very good. do fair Do. seconds a In h above data, indicates substantial iifiifiFifi???ifi fifi itjjjji:13::1: Z? 133 equivalence to the standard, good and very good indicate superior washing action, and p nd t p Washing a n. as om- With the same sulfonate and standard built pared to the washing action of the boveto contain sulfonate and 70% sodium sulscribed standard. fate, the following data were obtained at 110 F.:

Example 2 Foaming determinations were run by the 30 method of Ross and Miles (Oil and Soap 18,99 water, Water, (1941) The method consists of allowing 200 cc Semnds Seconds of the solution being tested to run out of a 0 standard orifice into a cylinder initially containsiiiiilFifi???ifi fifi ijij jiiijji::11 2% ii ing 50 cc of the same solution, and measuring the height of the foam generated immediately and after various time intervals. Constant tem- As demonstrated by the foregoing example it perature is maintained throughout the measureis preferred to employ the present alkyl benzene mentsulfonates as the essential detergent constituent Foammg games of 02% Solutlons m i 40 in a built composition, in which case the concenat on the ifi tration of the sulfonate is preferably about 30%, the 423454 Webster j q 2 if but may vary from about 10% to about 70%, it of e follows (the values being the height in centiig gg gi. g; i g 5 5333: gg g gg? meters after the indicated number of minutes) tageously be employed Without compounding with other ingredients. Heightinomimeters In order to illustrate the use of saturate petroleum fractions, a series of alkyl substituted 0 1 5 10 benzene sulfonates was prepared, using various saturate petroleum fractions from widely different 4,8464%webstersumate m 118 r The y 0nwa p r rm i a cor staiidard 9.5 17- ance with the aforementioned patent applications, the procedure being as follows: A contactor equipped with a stirrer was charged with is ig s ggsg iy gglz gg i ii g ifi g Value about 150 g. of benzene, about 150 g. of saturate, and about 134 g. of anhydrous hydrogen Example 3 fluoride. The material was stirred at room temx0e the sulfonate perature while about 75 g. of isobutylene was ing sggg i 32553331 53 S g; the following troduced over a period of 2 minutes. The stirred components: 30% sulfonate and 70% sodium sulfi i gg fgi fig g gg gg g giglgz fate The followmg results were obtamed' usually about 190 p. s. i. The contactor was then cooled to about 0 C. in an ice bath and the Height in Centimeters hydrogen fluoride removed. The acid and organic layers were separated and the organic layer 0 1 5 10 washed with water. The alkylated benzene product was recovered by distillation. 428464 F.Webster sulfonate 19.5 18.0 18.0 -3 Sulfonation was performed using either 100% Standard sulfuric acid or 20% oleum, as follows: To about 30 g. of the alkylbenzene in a 3-neck flask This detergent composition is especially valuequipped w stirrer, d pp n fu e d alable for washing wool, and from the present data 0mm Chloride tube Was added PW about 40 it is apparent that no loss in foaming value is evisf 0 Sulfuric ci ver a peri d f about denced by the present detergent 30 minutes. The stirred mixture was then Product Number Saturate 300-400" F. dearomatized Webster straight run. dearomatized Webster straight run. dearomatized Webster straight run. dearomatized Webster straight run. second-pass catalytic gas oil.

. second-pass catalytic gas oil.

second-pass catalytic gas oil. 410532 F. East Texas straight-am.

1 About 25% boiling above 500 F.

The standard used in the following examples was a. sodium alkyl benzene sulfonateprepared by a Friedel-Crafts reaction from a narrow range saturate, the sulfonate having a molecular weight range of from about 233 to about 263. For comparison, the molecular weight range of the prod-' uct represented by product No. 6 was from about 200 to 295. The standard used herein is believed the best detergent of the type heretofore available.

alkyl benzene sulfonate Example 5 The sodium alkyl benzene sulfonates represented above by product Nos. 1, 2, 5 and 6 were tested for dispersing power as follows:

To the original samples, which contained from about to active sulfonate content, was added sodium sulfate so that the'active sulfonate content of each was 25%. Measurements were with 0.2% of the sample, representing a final concentration of 0.05% of active sulfonate content. Distilled water was used throughout. The standard employed had about 40% active" sul', fonate content, representing a final concentration of 0.08% of active sulfonate content.

Soil was synthesized by impregnatingumber, which had passed a 200 mesh sieve, with an oil mixture containing 49.5% cottonseed oil, 49.5% medium viscosity mineral oil and 1.0% oleic acid. One gram of the oil mixture was dissolved in 25 cc. of benzene, 25 g. of umber added to the solution, and the whole stirred and dried until no benzene odor was detectable. The resulting oiled umber contained 1.98% mineral, 1.98% cottonseed (saponifiable) oil and 0.04% oleic acid, providing an acid soil with saponifiable and unsaponifiable fat.

An electric turbidimeter of the visual type was used for the test.

The test was performed as follows: 0.2 gm. samples of the oiled umber, each weighed to 0.01 gm., were placed in ml. beakers. 4 ml. of a 5% solution of the agent to be tested was added to the beaker and triturated with a glass rod until the umber was completely wetted. This mixture was washed into a ml. high form Nessler tube and diluted to the mark with distilled water. 25 glass beads were added to each tube, which was. then stoppered and inverted 25 times. After allowing the tubes to stand for two est tes l0 hours at 25 C. (or 50 C., as desired), 50 ml. was siphoned off from the middle portion into a turbidimeter tube, taking care not to disturb any suspended umber. The turbidimeter was adjusted until the filament image just vanished. The reading was taken at. this p i t.

The following results were obtained:

Dispersing power, percent of Standard Product Number 1 (300400 F. Webster) 58. 6 60.0 5 BOO-400 F. Cata1ytic).. 86. 5 64. 8 2 (400-500 F. Webster). 120. 0 128.6 6 (400-500 F. Catalytic) i 107. 8 124. 8 Standard 100 100 These data show the superiority of the 400-500 F. fraction over the 300-400 F. fraction, and also over the standard.

Example 6 Dispersing power, percent of Standard at 50 0.

Product Number 2-Grain ld-Grain Water Water 2 (100-500 F. Webster) 1 10].. 4 114. 5 2 (400-500" F. Websterfl. 102. 8 127. G 8 (410-532, F. East Texas) 3 115.5 155. 3 Standard 100 100 5: SCulfonatcd with 100% H25 04 at a temperature of from 25 C. to 5 2 Sulfonated with 20% oleum at a temperature of from 0 s C. to 25 C. 3 Sulfonated with 25 C.

100% H3804 at a temperature of from 0 C. to

These data demonstrate the high dispersing power of the present detergents. in both soft and hard water, and that similar results are obtained with petroleum fractions from widely different sources regardless of the mode of sulfonation.

Example 7 The detergents prepared in accordance with the present invention were tested against the standard in the actual washing of textiles.

Standard soiled test swatches were mechanically agitated in both soft (Z-grain) and hard (15-grain) water at 0.3 detergent concentration for cotton, and 0.4% for W001. Each detergent, including the standard, contained 25% active sulfonate content, the balance being sodium sulfate. Washing time was 15 minutes, followed by The following data were obtamed:

Cotton Wool Product number Soft Hard Soft Hard Water Water Water Water 2 (400500 F. Webster) 1 Fair Fair Very good. 2 (400500 F. Webster) 2 Good..." Good. 6 (400500 F. Catalytic) do Do. 8 (410532 F. East Texa .do. Fair. 3 (500-600" F. Webster)- Very goo Poor. 4 (600700 F. Webster) 3 Poor... Very poor. Very poor. 4 (GOO-700 F. Webster) 4 .do. d o Do. 7 (500-600 F. Catalytic) Fair. air Fair. (300400 F. Webster) 5 Poor Very poor- Very poor.

Sulfonated with 100% H2SO4 at 25 0. 55 0.

2 Sulfonated with 20% oleum at C. to 25 C.

3 Sulfonated with 100% H2804 at 0C. to 25 C.

4 Sulfonatcd with 20% oleum at 0 C.

Alkylation of naphthalene instead of benzene.

In'the above data, fair indicates substantial equivalence to the standard, good and very good indicate superior washing action, and poor and very poor indicate poor washing action. These data show the products of the present invention, indicated by product Nos. 2, 6 and 3, to be from fair to very good in each test. Other products, such as product No. 3, may be very good in one test, and very poor in another.

In general, the crude alkyl benzene sulfonates prepared in accordance with the present invention are in sufficient concentration so that purification thereof is unnecessary, and additional agents may be added to the crude product. If desired, however, the sulfonate may be concentrated by purification, such as by extraction with alcohol. Other materials which may enhance the products may then be added, and the concentration of the sulfonate so adjusted to the desired value. Thus, trisodium polyphosphates may advantageously be added for some purposes.

Alkalies other than sodium hydroxide may be employed in the preparation of the sulfonate, such as the hydroxides of potassium, and ammonia.

We claim:

A detergent composition comprising as its essential detergent constituent a mixture of alkyl benzene sulfonates obtained by alkylating benzene with a petroleum fraction containing a substantial proportion of saturate hydrocarbons having at least one tertiary hydrogen atom per molecule, an aromatic hydrocarbon content of less than about 35%, and having a boiling range of from about 400 F. to 500 F., said alkylation being performed by reacting, at a temperature of from 50 C. to 200? C. and pressure of from 100 to 200 p. s. i., benzene with said petroleum fraction by subjecting a mixture of benzene and said to aromatic hydrocarbons is from 1:5 to 6:1, the

petroleum fraction to the simultaneous action of hydrogen fluoride and a material selected from the groupconsisting of a tertiary mono-folefin having no more than 9 carbon atoms and a tertiary alkyl substituted aromatic hydrocarbon, wherein the mole ratio of saturate hydrocarbons mole ratio of said material selected from the group consisting of a tertiary mono-olefin and a tertiary alkyl substituted aromatic hydrocarbon to benzene plus saturate hydrocarbons is from 1:10 to 1:1 and the mole ratio of hydrogen fluoride to aromatic hydrocarbons plus saturate hydrocarbons is from 1:1 to 8:1, separating the: alkylated benzene product wherein the alkyl group; attached to the benzene nucleus contains the same number of carbon atoms as the saturate hydrocarbons containing a tertiary hydrogen atom of said pertoleum fraction, sulfonating said alkylated. benzene product to form a monosulfonated alkyl benzene, and converting the sulfonated product to an alkali metal salt. 7

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